CN102079695A - Method for catalytically oxidizing cyclohexane - Google Patents
Method for catalytically oxidizing cyclohexane Download PDFInfo
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- CN102079695A CN102079695A CN2009102498307A CN200910249830A CN102079695A CN 102079695 A CN102079695 A CN 102079695A CN 2009102498307 A CN2009102498307 A CN 2009102498307A CN 200910249830 A CN200910249830 A CN 200910249830A CN 102079695 A CN102079695 A CN 102079695A
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Abstract
The invention discloses a method for catalytically oxidizing cyclohexane, which is characterized in that cyclohexane, hydrogen peroxide and a catalyst are in contact for reacting, the mol ratio of the cyclohexane to the hydrogen peroxide is 0.5-8, the concentration of the catalyst in a reaction system is 0.005-0.1g/min, the reaction temperature is 40-150 DEG C, the catalyst is a titanium-silicon molecular sieve with an MFI structure, a hysteresis loop exits between an adsorption isotherm and a desorption isotherm of low-temperature nitrogen absorption of the molecular sieve, a crystalline grain is a single hollow crystalline grain or an aggregated crystalline grain formed by the aggregation of a plurality of hollow crystalline grains, the radial length of the cavity part of the hollow crystalline grains is 5-300nm, and the benzene adsorption capacity of the sample of the molecular sieve, measured under the conditions that the absorption time is 1h, the temperature is 25 DEG C and P/P0 is equal to 0.10, is at least 70mg/g. The method has the advantages of high selectivity of a target product and environment protection.
Description
Technical field
The present invention relates to a kind ofly make catalyzer with HTS, the method for the catalyzed oxidation hexanaphthene of hydrogen peroxide as oxidant.
Background technology
Pimelinketone, hexalin are important chemical material, are widely used in the industry of fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent.Particularly because the developing rapidly of polymeric amide industry, as the demand of the pimelinketone of preparation nylon 6 and nylon 66 intermediates, hexalin whole world every year all more than 1,000,000 tons.The cyclohexanone production process route mainly contains three kinds: cyclohexane liquid-phase oxidation method, phenol hydrogenation method and benzene partial hydrogenation method, wherein cyclohexane oxidation process is the main process of industrial production pimelinketone, account for more than 90%, but this process also is considered to minimum one of efficient in all chemical industry processes.The process of cyclohexane oxidation process synthesizing cyclohexanone is one of the restriction key of caprolactam production and bottleneck.
At present, utilize the cyclohexane liquid-phase oxidation preparing cyclohexanone to mainly contain three kinds of industrial technologies and method: non-catalyst oxidation method, boric acid class catalytic oxidation and cobalt salt catalytic oxidation.
The non-catalyst oxidation method is one of main technique technology that adopts both at home and abroad at present.This technology cyclohexane conversion is 3%～5%, and hexalin and cyclohexanone mixture overall selectivity are about 80%.This method by catalytic dehydrogenation, can make hexalin be converted into pimelinketone under zinc oxide or copper, zinc oxide catalyst action.The certain embodiments per pass conversion is about 60%, and selectivity reaches 99%.Product obtains the pimelinketone product of 60% left and right sides purity after condensation separation.The characteristics of this method are: the oxidizing process condition comparatively relaxes, and slagging scorification is less, and cycle of operation is long.The ratio of hexalin and pimelinketone is 1.0: 1.2 in the product, and the relative content of hexalin is lower, has alleviated the load of cyclohexanol dehydrogenation process to a certain extent.Compare with the phenol raw material, adopting hexanaphthene is that raw material has the comparatively cheap advantage of price, and Technology is ripe.But exist tangible deficiency, longer as operational path, the hexanaphthene internal circulating load is big, and the energy consumption height pollutes also greatlyyer, and particularly in the cyclohexyl hydroperoxide decomposition course, pimelinketone, hexalin selectivity are relatively poor, and yield is low.In addition, a large amount of waste lyes that this process produces, difficult treatment is still a global environmental protection difficult problem so far.
The cyclohexane conversion of boric acid class catalytic oxidation reaches at 10%～12% o'clock, and the alcohol ketone selectivity is 90%, and the ratio of hexalin and pimelinketone is 10: 1 in the product.It is too high to generate the hexalin ratio, and the certain embodiments burden is big, the energy consumption height.The deadly defect of this method is to have increased boric acid ester hydrolysis and boric acid recovery system, initial cost height, catalyzer dewatering and recovery boric acid in service are very complicated, and operation easier is big, and boric acid catalyst is easy to cause equipment and pipeline seriously to stop up, and has influenced this The Application of Technology and development.
The cobalt salt catalytic oxidation can be controlled the composition of reactant to a certain extent, and the ratio of hexalin and pimelinketone is about 65: 35 in the general product.Catalysis of cobalt salt can not only shorten the inductive phase of reaction, improves the purpose product selectivity, and can make hydrocarbon oxide that cyclohexane oxidation generates when degenerating branch, has quickened the carrying out of reaction.But the part by product can generate the scoriform thing with cobalt ion reaction, is deposited on the equipment pipe inwall and causes obstruction.
Utilizing common HTS to make catalyzer, hydrogen peroxide as oxidant carries out in the research report that cyclohexane oxidation prepares pimelinketone low, the poor selectivity of cyclohexane conversion.
Summary of the invention
The inventor discloses a kind of MFI of having structure of hollow HTS first in CN1301599A, this molecular sieve has unique duct, and crystal grain is hollow structure.Therefore, the purpose of this invention is to provide a kind of is the method that the catalyst cyclohexane oxidation is produced pimelinketone, hexalin with the novel hollow HTS.
A kind of method of catalyzed oxidation hexanaphthene, it is characterized in that hexanaphthene, hydrogen peroxide and catalyzer contact reacts, the mol ratio of hexanaphthene and hydrogen peroxide is 0.5～8, catalyst concn is 0.005～0.1g/ml in the reaction system, 40～150 ℃ of temperature of reaction, said catalyzer is the HTS with MFI structure, have hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen of this molecular sieve absorption and the desorption isotherm, crystal grain is one hollow crystal grain or the gathering crystal grain that is gathered into by a plurality of hollow crystal grain; The radical length of the cavity part of this hollow crystal grain is 5～300 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is at least 70 milligrams/gram.
In the method provided by the invention, that is adopted has a MFI structure of hollow HTS, discloses in CN1301599A, and this patent documentation is incorporated herein by reference.
In the method provided by the invention, in the reaction system solvent can also be arranged, used solvent comprises ketone or alcohols, and the wherein preferred again acetone or the trimethyl carbinol are as solvent, and the mol ratio of solvent and hexanaphthene is preferably and is not more than 10.
It needs to be noted, the inventive method can be under condition of no solvent, introducing and hexanaphthene volume ratio are 0.0000001～0.01 emulsifying agent, after introducing emulsifying agent, improve the mixedness between reactant on the one hand, strengthen diffusion, improve speed of reaction, can prolong catalyst life on the other hand, make the steady running time of this method prolong greatly.Simultaneously, after introducing emulsifying agent, need not solvent in the reaction system, then separation costs, energy consumption etc. lower greatly, have simplified reaction, make the easier control of entire reaction, are beneficial to suitability for industrialized production and application.In method provided by the invention, emulsifying agent is selected from one or more in polybenzimidazole, polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, poly derivative and the tensio-active agent.
More particularly, the said emulsifying agent of the present invention can be selected from the polybenzimidazole pyrrolidone, polybenzimidazole alcohol, the polybenzimidazole ether, the polybenzimidazole pyrimidine, the polypropylene pyrrolidone, POLYPROPYLENE GLYCOL, the polypropylene ether, the polypropylene pyrimidine, the polyoxyethylene glycol pyrrolidone, the polyoxyethylene glycol ether, the polyoxyethylene glycol pyrimidine, the polystyrene pyrrolidone, polystyrene alcohol, the polystyrene ether, the polystyrene pyrimidine, the polyvinyl chloride pyrrolidone, polyvinyl chloride alcohol, the polyvinyl chloride ether, the polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, in polyvinyl ethyl ether and the polyethylene pyrimidine one or more.
Said tensio-active agent can be cetyl trimethylammonium bromide, dodecyl dimethyl ammonia chloride, fatty alcohol-polyoxyethylene ether, block polyoxyethylene polyoxypropylene ether, alkylol amide, polyol ester class, tween series, sapn series, fluorocarbon surfactant series.
In the method provided by the invention, the mol ratio of hexanaphthene and hydrogen peroxide is preferably 0.8～6, and the mol ratio of solvent and hexanaphthene is preferably and is not more than 8, and catalyst concn is preferably 0.005～0.08g/ml, and preferred temperature of reaction is 50～120 ℃.
The present invention adopts hollow HTS as the catalyst activity component, has increased the velocity of diffusion of reactant and product, has reduced the generation of side reaction, and its catalytic oxidation activity and selectivity obviously improve.Especially after introducing emulsifying agent, catalytic activity and activity stability are better.
The method of catalyzed oxidation hexanaphthene provided by the invention has solved problems such as common HTS activity is lower.Technology of the present invention is simple, purpose selectivity of product height; Catalyst activity, stability height, regenerability is good; Because used oxygenant is a hydrogen peroxide, oxidation products generates water, and environmentally safe is a good Green Chemistry process, has better industrial application prospects.
Embodiment
Following embodiment will the present invention is further illustrated, but therefore do not limit the present invention.
Used reagent is commercially available chemically pure reagent among Comparative Examples and the embodiment.
Used traditional HTS (TS-1) is (TS-1) sieve sample of preparing by the method described in the prior art [CyclohexaneOxidation Catalyzed by Titanium Silicalite (TS-1) With Hydrogen Peroxide Journalof Natural Gas Chemistry 2001,10 (4): 295-307] in the Comparative Examples.
Used hollow HTS HTS is that (Hunan is built long company and made for the Industrial products of the described HTS of Chinese patent CN1301599A among the embodiment, through the X-ray diffraction analysis is the HTS of MFI structure, have hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this molecular sieve and the desorption isotherm, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is 78 a milligrams/gram).
In Comparative Examples and embodiment:
Cyclohexane conversion (%)=(hexanaphthene molar content in the 1-product) * 100;
Pimelinketone, hexalin selectivity (%)=(in the product in pimelinketone molar content+product hexalin molar content)/(hexanaphthene molar content in the 1-product) * 100.
Comparative Examples 1:
The situation of non-activity when this Comparative Examples explanation reaction does not add catalyzer.
The hydrogen peroxide that in three mouthfuls of vials of 250ml, adds 0.74mol (closing 80ml) hexanaphthene and 0.6mol 30% (closing 80ml) successively.Encloses container is put in temperature is controlled in 80 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 4 hours, conversion of cyclohexane is 0.
Embodiment 1
Take by weighing the hollow HTS HTS of 4g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of 0.74mol (closing 80ml) hexanaphthene and 0.6mol 28% (closing 80ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 80 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 9.6%, and pimelinketone, hexalin selectivity reach 86.1%.
Embodiment 2
Take by weighing the hollow HTS HTS of 4g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of the 100ml trimethyl carbinol, 0.19mol hexanaphthene (about 20ml) and 0.15mol 28% (closing 20ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 70 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 9.1%, and pimelinketone, hexalin selectivity reach 82.6%.
Comparative Examples 2
Take by weighing the common titanium-silicon molecular sieve TS-1 of 4g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of the 100ml trimethyl carbinol, 0.19mol hexanaphthene (about 20ml) and 0.15mol 28% (closing 20ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 70 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 6.9%, and pimelinketone, hexalin selectivity reach 72.4%.
Embodiment 3
Take by weighing the hollow HTS HTS of 4g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of the 100ml trimethyl carbinol, 0.19mol hexanaphthene (about 20ml) and 0.15mol 28% (closing 20ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 80 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 17.9%, and pimelinketone, hexalin selectivity reach 82.6%.
Comparative Examples 3
Take by weighing the common titanium-silicon molecular sieve TS-1 of 4g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of the 100ml trimethyl carbinol, 0.19mol hexanaphthene (about 20ml) and 0.15mol 28% (closing 20ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 80 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 8.9%, and pimelinketone, hexalin selectivity reach 68.5%.
Embodiment 4
Take by weighing the hollow HTS HTS of 4g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of the 120ml trimethyl carbinol, 0.37mol hexanaphthene (about 40ml) and 0.1mol 28% (closing 14ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 100 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 1 hour, conversion of cyclohexane is 8.4%, and pimelinketone, hexalin selectivity reach 81.2%.
Embodiment 5
Take by weighing the hollow HTS HTS of 1g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of the 150ml trimethyl carbinol, 0.19mol hexanaphthene (about 20ml) and 0.15mol 28% (closing 20ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 100 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 8 hours, conversion of cyclohexane is 7.3%, and pimelinketone, hexalin selectivity reach 85.6%.
Embodiment 6
Take by weighing the hollow HTS HTS of 0.3g and be loaded in three mouthfuls of vials of 100ml, in container, add the hydrogen peroxide of the 45ml trimethyl carbinol, 0.06mol hexanaphthene (about 6ml) and 0.05mol 30% (closing 6ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 50 ℃ the water bath with thermostatic control, water-bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 10 hours, conversion of cyclohexane is 8.2%, and pimelinketone, hexalin selectivity reach 81.3%.
Embodiment 7
Take by weighing the hollow HTS HTS of 2g and be loaded in the 500ml reactor, in container, add the hydrogen peroxide of the 300ml trimethyl carbinol, 0.37mol hexanaphthene (about 40ml) and 0.32mol 30% (closing 40ml) more successively.Temperature is controlled at 100 ℃.Start and stir, begin reaction.
React after 4 hours, conversion of cyclohexane is 18.2%, and pimelinketone, hexalin selectivity reach 87.4%.
Embodiment 8
Take by weighing the hollow HTS HTS of 2g and be loaded in the 500ml reactor, in container, add the hydrogen peroxide of the 300ml trimethyl carbinol, 0.37mol hexanaphthene (about 40ml) and 0.32mol 30% (closing 40ml) more successively.Temperature is controlled at 120 ℃.Start and stir, begin reaction.
React after 4 hours, conversion of cyclohexane is 6.2%, and pimelinketone, hexalin selectivity reach 85.2%.
Embodiment 9
Take by weighing the hollow HTS HTS of 4g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of the 100ml trimethyl carbinol, 0.19mol hexanaphthene (about 20ml) and 0.225mol 28% (closing 30ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 80 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 0.5 hour, conversion of cyclohexane is 10.9%, and pimelinketone, hexalin selectivity reach 82.1%.
Embodiment 10
Take by weighing the hollow HTS HTS of 8g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of 100ml acetone, 0.38mol hexanaphthene (about 40ml) and 0.075mol 28% (closing 10ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 100 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 7.5%, and pimelinketone, hexalin selectivity reach 86.3%.
Comparative Examples 4
Take by weighing the common titanium-silicon molecular sieve TS-1 of 8g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of 100ml acetone, 0.38mol hexanaphthene (about 40ml) and 0.075mol 28% (closing 10ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 100 ℃ the constant temperature oil bath, oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 6.8%, and pimelinketone, hexalin selectivity reach 66.1%.
Embodiment 11
The present embodiment explanation is solvent-free, the reaction process of introducing emulsifying agent.
Take by weighing the hollow HTS HTS of 4g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of 0.74mol (being roughly equal to 80ml) hexanaphthene and 0.6mol 28% (being roughly equal to 80ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 80 ℃ the constant temperature oil bath, introducing simultaneously with the hexanaphthene volume ratio is 0.001 emulsifier tween 60, and oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 26.6%, and pimelinketone, hexalin selectivity reach 89.6%.
React after 24 hours, conversion of cyclohexane is 25.8%, and pimelinketone, hexalin selectivity reach 88.3%.
Embodiment 12
The present embodiment explanation is solvent-free, the reaction process of introducing emulsifying agent.
Take by weighing the hollow HTS HTS of 2g and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of 0.37mol (being roughly equal to 40ml) hexanaphthene and 0.74mol 28% (being roughly equal to 100ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 80 ℃ the constant temperature oil bath, introducing with the hexanaphthene volume ratio is 0.0001 emulsifying agent polybenzimidazole pyrrolidone, and oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 48.3%, and pimelinketone, hexalin selectivity reach 89.8%.
React after 24 hours, conversion of cyclohexane is 47.8%, and pimelinketone, hexalin selectivity reach 88.6%.
Comparative Examples 5
This Comparative Examples explanation with general T S-1 HTS is being catalyzer, solvent-free, the situation of introducing emulsifying agent.
Take by weighing the 2g titanium-silicon molecular sieve TS-1 and be loaded in three mouthfuls of vials of 250ml, in container, add the hydrogen peroxide of 0.37mol (being roughly equal to 40ml) hexanaphthene and 0.74mol 28% (being roughly equal to 100ml) more successively.Three mouthfuls of vials are put in temperature are controlled in 80 ℃ the constant temperature oil bath, introducing with the hexanaphthene volume ratio is 0.0001 emulsifying agent polybenzimidazole pyrrolidone, and oil bath places on the temperature control magnetic stirring apparatus.Start magnetic agitation, begin reaction.
React after 6 hours, conversion of cyclohexane is 25.7%, and pimelinketone, hexalin selectivity reach 74.4%.
React after 24 hours, conversion of cyclohexane is 15.2%, and pimelinketone, hexalin selectivity reach 64.3%.
Claims (8)
1. the method for a catalyzed oxidation hexanaphthene; it is characterized in that hexanaphthene; hydrogen peroxide and catalyzer contact reacts; the mol ratio of hexanaphthene and hydrogen peroxide is 0.5～8; catalyst concn is 0.005～0.1g/ml in the reaction system; 40～150 ℃ of temperature of reaction; said catalyzer is the HTS with MFI structure; there is hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of this molecular sieve and the desorption isotherm; crystal grain is one hollow crystal grain or the gathering crystal grain that is gathered into by a plurality of hollow crystal grain; the radical length of the cavity part of hollow crystal grain is 5～300 nanometers; this molecular sieve is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under 1 hour the condition of adsorption time is at least 70 milligrams/gram.
2. according to the method for claim 1, it is characterized in that also containing solvent in the reaction system, the volume ratio of solvent and hexanaphthene is for being not more than 10.
3. according to the method for claim 2, wherein, solvent is the acetone or the trimethyl carbinol.
4. according to the process of claim 1 wherein, the mol ratio of hexanaphthene and hydrogen peroxide is 0.8～6, and catalyst concn is 0.005～0.08g/ml in the reaction system.
5. according to the method for claim 1, it is characterized in that adding a kind of emulsifying agent when not containing solvent in the reaction system, the volume ratio of emulsifying agent and hexanaphthene is 0.0000001～0.01.
6. according to the method for claim 5, wherein said emulsifying agent is selected from one or more in polybenzimidazole, polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, poly derivative and the tensio-active agent.
7. according to the method for claim 5, wherein said emulsifying agent is selected from the polybenzimidazole pyrrolidone, polybenzimidazole alcohol, the polybenzimidazole ether, the polybenzimidazole pyrimidine, the polypropylene pyrrolidone, POLYPROPYLENE GLYCOL, the polypropylene ether, the polypropylene pyrimidine, the polyoxyethylene glycol pyrrolidone, the polyoxyethylene glycol ether, the polyoxyethylene glycol pyrimidine, the polystyrene pyrrolidone, polystyrene alcohol, the polystyrene ether, the polystyrene pyrimidine, the polyvinyl chloride pyrrolidone, polyvinyl chloride alcohol, the polyvinyl chloride ether, the polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, in polyvinyl ethyl ether and the polyethylene pyrimidine one or more.
8. according to the method for claim 6, wherein said tensio-active agent is selected from cetyl trimethylammonium bromide, dodecyl dimethyl ammonia chloride, fatty alcohol-polyoxyethylene ether, block polyoxyethylene polyoxypropylene ether, alkylol amide, polyol ester class, tween series, sapn series, fluorocarbon surfactant series.
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| CN103204769A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Method for production of cyclohexanone from cyclohexanol |
| CN103373975A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Oxidation method of cycloparaffin |
| CN103420869A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Method of ammoxidation of cyclohexane |
| CN103508845A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Method for oxidizing cyclohexane |
| WO2014015491A1 (en) * | 2012-07-26 | 2014-01-30 | Rhodia Operations | Cycloalkane oxidation catalysts and method to produce alcohols and ketones |
| US8940939B2 (en) | 2011-05-05 | 2015-01-27 | China Petroleum & Chemical Corporation | Process of oxidizing cyclohexane |
| CN105523910A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Oxidation method for cyclohexane |
| CN109721467A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | The method for preparing halohydrin |
| CN112175415A (en) * | 2020-09-24 | 2021-01-05 | 宁波润禾高新材料科技股份有限公司 | Water-insoluble pigment dispersion stabilizer and preparation method thereof |
| CN116120157A (en) * | 2023-02-24 | 2023-05-16 | 山东京博石油化工有限公司 | Method for preparing cyclopentanone by selective oxidation of cyclopentane |
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| US8940939B2 (en) | 2011-05-05 | 2015-01-27 | China Petroleum & Chemical Corporation | Process of oxidizing cyclohexane |
| CN103204769B (en) * | 2012-01-13 | 2015-03-18 | 中国石油化工股份有限公司 | Method for production of cyclohexanone from cyclohexanol |
| CN103204769A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Method for production of cyclohexanone from cyclohexanol |
| CN103373975A (en) * | 2012-04-27 | 2013-10-30 | 中国石油化工股份有限公司 | Oxidation method of cycloparaffin |
| CN103373975B (en) * | 2012-04-27 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of Oxidation method of cycloparaffin |
| CN103420869A (en) * | 2012-05-23 | 2013-12-04 | 中国石油化工股份有限公司 | Method of ammoxidation of cyclohexane |
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